JPS6137892A - Liquid crystal composition - Google Patents

Abstract

PURPOSE:A liquid crystal compsn. stable to water for a long period of time and suitable for a display device, etc., which is obtd. by mixing a hydroxyl group- contg. polymer, an org. compd. contg. a straight-chain hydrophobic group and a quaternary ammonium group, and a borate. CONSTITUTION:A polymer (A) having a repeating unit of formula I, such as saponified ethylenevinyl acetate copolymer or polyvinyl alcohol, an org. compd. (B) having two or three straight-chain hydrophobic groups or at least one straight-chain hydrophobic group contg. a rigid portion in the chain and having a quaternary ammonium group, such as a compd. of formula II, and a borate (C) such as Na orthoborate are mixed to prepare the purpose liquid crystal compsn. It is pref. to mix the components A, B and C in such a proportion that the wt. ratio of A to B is 0.1-0.9 and the equivalent ratio of C to the repeating unit of formula I in A is 0.005-0.1.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-stabilized liquid crystalline composition comprising a specific polymer, a specific organic compound, and a specific inorganic salt. For more details, ill 4CH2-CH+
A heavy compound having a repeating unit shown in
B) A liquid crystalline composition comprising an organic compound having at least one straight-chain hydrophobic group containing a rigid moiety in a chain, and (c) having a +i-th ammonium group, and (3) a borate. .

Energy intake and metabolite processing in living organisms are carried out through biological membranes. In recent years, research on synthetic organic compounds similar to biological membranes has been progressing, and it has been reported that some compounds with linear hydrophobic groups and ionic groups have stable liquid crystal structures in water. There is. These synthetic organic compounds with liquid crystallinity have functions similar to those of biological membranes, such as phase transition, phase separation, and organic molecule adsorption, and have shown potential as synthetic biological membranes. [7]However, the liquid crystal structure formed by the above-mentioned synthetic organic compound is obtained by dispersing the above-mentioned synthetic organic compound in water and existing in a state similar to that of concentrated soapy water.
It is extremely difficult to use it practically in this form. Therefore, attempts have been made to immobilize the aforementioned synthetic organic compounds to facilitate their handling while maintaining functions similar to those of biological membranes. In seven of the methods, the synthetic organic compound described above is mixed with polyvinyl alcohol and formed into a membrane.

(Chemistry Letters, Otsu 25
-Ro2 Otsu (/ 9g3 Gphemlstry Let
ters, 7/7-720 (/9g4')
) The liquid crystal structure of the synthetic organic compound is maintained in these film-like materials, and the film-like materials exhibit liquid crystallinity.

However, the constituent components of these membrane-like materials are water-soluble, and they have the disadvantage that when the membrane-like materials are used in water, the constituent components are redissolved. Radiation irradiation is used as a method of making these film-like substances unbathable. (Proceedings of the 9th Spring Annual Meeting of the Japan Ihi Society, 6 otsu 0 (/'?zag)). However, it lacks versatility because it requires special equipment. Although a method of coating the shredded membrane with cellulose acetate has been carried out (Proceedings of the Society of Polymer Science and Technology, 3200°2g3-2g'1g (19g3)), sufficient water resistance has not been obtained.

In order to solve the above-mentioned drawbacks and obtain a liquid crystalline composition with water resistance that can be used practically, the present inventors conducted research H. By using borate in a composition consisting of a synthetic organic compound, the constituent substances could be reduced in water. The inventors have completed the present invention by discovering a liquid crystalline composition that exhibits extremely little elution and fully functions as a liquid crystal.

10. The present invention provides a heavy "H" polymer having a repeating unit represented by +11 4CH2-C++ (2) (a) containing two or three @ chain hydrophobic groups, or (b) a rigid moiety in the chain A liquid crystal composition having at least one linear hydrophobic group, and comprising (c) an organic compound having a 7th class ammonium group, and (3) a borate salt.

It is known that borate can be used as a gelling agent for polyvinyl alcohol, but when polyvinyl alcohol alone is glued with borate, it lacks long-term water resistance and dissolves during repeated use. It was something to do. However, when a specific organic compound is present as in the present invention, the reason is not clear, but it can be predicted from the conventional knowledge that the resulting composition is stabilized in water and can withstand repeated use over a long period of time. Excellent properties that are not commonly used have been expressed.

One of the components of the liquid crystal composition of the present invention is a polymer having a repeating unit represented by 4c+2-C++ (hereinafter abbreviated as hydroxyl group polymer). The combination is 4cH2-c
Repetition 1, indicated by ++. Any H unit may be used as long as it has H units, but considering the compatibility between the hydroxyl group polymer and other components of the liquid crystal composition of the present invention, the hydroxyl group polymer is 4C) I-C++
It is preferable to contain 50% by weight or more of repeating units represented by H 2 . More preferable]7〈is 4CH-C
It is preferable to use a polymer containing 70% by weight or more of 1.2 units of repeating units represented by ++ in an amount of 70% by weight or more by weight of gO.

Considering the mechanical strength of the liquid crystal composition, the molecular weight of the hydroxyl group-containing polymer used in the present invention is s, oo
o~SOO million, more preferably io, ooo
~1 million is preferably used.

Specific examples of the hydroxyl group-containing polymer preferably used in the present invention are as follows.

Fully saponified and partially saponified products of vinyl esters, as well as their partially formal and acetal products,
Partial ester products: Completely saponified products and partially saponified products of copolymers of vinyl esters and ethylenic monomers, as well as their partially formalized products, partially acetalized products, and partially ester products, etc. can be mentioned. Here, specific examples of vinyl esters include, for example, vinyl formate,
Examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl crotonate, vinyl caprylate, and the like. It's Kade.
The ethylenic monomer copolymerized with vinyl esters is not particularly limited, and known ones can be used. Typical ethylenic monomers that are generally suitably used include α-olefins such as ethylene and propyrene; vinyl halides such as vinyl chloride and vinyl bromide; nitriles such as acrylonitrile; Acrylic acid esters such as methyl diacrylate and ethyl acrylate; Methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; Vinyl monomers containing amide groups such as diacrylamide, methacrylamide, and vinylpyrrolidone; acrylic acid and methacrylic acid Vinyl Cal? Acids and their salts; Vinyl radical acids such as maleic acid, fumaric acid, itaconic acid, their esters and their esters: Itaconic anhydride: Maleic anhydride 1
etc."'Acid anhydride'1": 2-471J"77ゝ-4-""
Sulfonic acids such as propane sulfonic acid, ethylene sulfonic acid, ester sulfonic acid, methallyl sulfonic acid, and styrene sulfonic acid, and salts thereof may be mentioned.

Considering the compatibility of each component of the resulting liquid crystal composition, the above-mentioned ethylenic monomer preferably accounts for 80% by weight or less in the hydroxyl group-containing polymer.

The hydroxyl group-containing polymer used in the present invention can be obtained by polymerizing a monomer having a group that can be converted into a hydroxyl group, and then converting the group that can be converted into a hydroxyl group into a hydroxyl group to obtain a repeating group represented by +CH-C++H. A polymer having units may also be used.

Another component of the liquid crystal composition of the present invention is 2 or 3
An organic compound having at least one linear hydrophobic group containing a straight M-chain hydrophobic group, a flexible and rigid part in the chain, and a tertiary ammonium group (liquid crystal properties and availability of raw materials). A straight chain alkyl group having q to 30 carbon atoms or a halodane-substituted group thereof is preferable for ease of It is also used in a sense that includes a branched type having up to 100 branches.

One of the linear organic compounds of the present invention has one or three linear hydrophobic groups. When the number of linear hydrophobic groups is one, the hydrophobicity is insufficient and the resulting composition is difficult to become liquid crystalline. When the number of linear hydrophobic groups is 9 or more, it is difficult to obtain raw materials for producing the liquid crystalline composition.

Another linear organic compound of the present invention has at least seven linear hydrophobic groups including a rigid portion in the chain.

In the present invention, the rigid moiety refers to the groups shown in the following (1), (2) and (2).

■ Divalent groups consisting of at least two aromatic rings connected directly or via carbon-carbon multiple bonds, carbon-nitrogen multiple bonds, nitrogen-nitrogen multiple bonds, ester bonds, amide bonds, etc. Specific examples of such groups include divalent groups such as .

■ A divalent group in which two aromatic rings have multiple bonds or a single bond between multiple atoms, and the rotation of the bond is energetically constrained. Specific examples of such groups include: For example, CH.

Examples include divalent groups such as.

■ A divalent group in which aromatic rings form a condensed ring [7], and when this condensed ring is stacked between multiple molecules, the rotation is sterically constrained to each other. Examples include covalent groups such as:

The number of carbon atoms in the straight chain hydrophobic group of a straight chain organic compound having at least one 10-armor hydrophobic group containing a rigid part in the chain is determined by the number of carbon atoms in the straight chain hydrophobic group of the straight chain hydrophobic group including the rigid part and the bond between the rigid part and the straight chain hydrophobic group. It means the number of carbon atoms in the part excluding the part. The bond between the rigid portion and the linear hydrophobic group is generally preferably a carbon-carbon single bond, an ester bond, or an ether bond.

A straight-chain hydrophobic group containing a rigid part in the chain has the following properties:
Further, from the viewpoint of stability of the liquid crystal composition, it is most preferable that water is contained in the linear organic compound.

The number of quaternary ammonium groups contained in the linear organic compound of the present invention is preferably one from the viewpoint of moldability of the obtained liquid crystal composition.

The linear organic compound of the present invention is not particularly limited as long as it satisfies the above requirements, and known compounds can be used.

Representative ones that are generally suitably used are specifically shown below.

However, R1 and R2 are the same or different straight chain alkyl groups having 6 to 30 carbon atoms or halogen-substituted products thereof, and R3, R
4 is the same or different alkyl group having 1 to 2 carbon atoms, or a substitute thereof with a halodane atom and/or a hydroxyl group.

However, [2, R1, and R2 are the same as above, and A is a positive integer. ), and hl 1 is a positive integer. R,R.

R5 is the same as described for R3 and R4 above.

OR' However, R1, R2, R3, R4, R5 and A are the same as above, 2 is l or 2, and m is θ or /.

However, R1, R2, R5, R4 and R5 are the same as above, and n is a positive integer.

However, R, R and R are the same as above, and R6 is an alkyl group having a carbon number of 1/L to 3θ, an alkyloxy group, or the alkyloxycar is a nyl group or a halodane-substituted product thereof, and CH.

p is θ and father is l. )E is +CH2-)T or ~o
-(CH2-57-Th. (However, ql is a positive integer.)) In the above general formulas [8), [D) and [E], k%ns Q
and " may be positive integers, but generally from the viewpoint of ease of obtaining raw materials, it is preferably 16. In addition, in the above general formula (B), h and 1 represent positive integers. However, in general, due to the ease of obtaining raw materials, /-1
It is preferable that Furthermore, the above general formula [A]% [
B], [C], [O] and [E], R1, R2, R3
The halogen atom of the halodane-substituted alkyl group represented by , R, R, and R includes fluorine, chlorine, bromine, and iodine atoms.

Seven other ingredients of the invention are borates. The borate mentioned here is not particularly limited, and known ones can be used. In general, considering crosslinking reactivity with hydroxyl group-containing polymers and water solubility of borates, orthoborates such as potassium orthoborate and sodium orthoborate; diborates such as sodium diborate and potassium diborate; Metaborate salts such as sodium acid and potassium metaborate @
: Tetraborate such as sodium tetraborate, potassium tetraborate, etc.
Acid salts: Pentaborate salts such as sodium pentaborate and potassium pentaborate are preferably employed. In particular, when an alkali metal tetraborate salt such as lithium tetraborate, sodium tetraborate, or potassium tetraborate is used, the resulting composition has the best water resistance.

The composition of the hydroxyl group-containing polymer and direct button organic compound, which are the components of the liquid crystalline composition of the present invention, is generally determined by considering the liquid crystallinity and strong properties of the resulting composition. The weight ratio of organic compounds is 0. l~0. q is more preferably o, and a range of ti to 01g is suitably employed.

The composition of the hydroxyl-containing polymer and borate, which are the components of the liquid crystal composition of the present invention, is generally determined by considering the water resistance of the resulting composition.
-CH+ 0.005 to 0.1 times equivalent on day 0, preferably 0.07 to 0.1 times equivalent to the repeating unit represented by -CH+
0.05 times equivalent of borate is used.

The method for producing the liquid crystal composition of the present invention is not particularly limited, and any method may be used. Examples of generally preferred iM manufacturing methods are as follows.

That is, the width of the hydroxyl group-containing polymer and iI! A method in which chain organic compounds are mixed in a solvent that dissolves them, solidified by solvent evaporation to obtain a composition, and then immersed in an aqueous borate solution. The method of mixing the hydroxyl group-containing polymer and the @boron organic compound is not particularly limited, and any method may be used. Generally, a method in which a predetermined amount of a hydroxyl group-containing polymer and a linear organic compound are dissolved in a solvent is suitable. The most suitable solvent to be used is water, but water-miscible organic solvents such as methanol, ethanol, acetone, dimethylformyl, tetrahydrofuran, dioxane, etc. It can be included as long as the chain organic compound is dissolved. The borate bath solution used here has a borate concentration of 0.1% by weight or more, preferably 0.1% by weight or more, depending on the bath solubility of the borate used, but considering the water resistance of the resulting liquid crystal composition. A content of 1% by weight or more is preferably employed. At this time, in order to prevent dissolution of the hydroxyl group-containing polymer and linear organic compound at the initial stage of immersion, other electrolytes such as sodium odor, potassium odor, sodium chloride, potassium chloride, sulfuric acid are added to the borate aqueous solution. It is preferable to dissolve an alkali metal salt such as sodium or potassium sulfate at a concentration of usually 20% by weight. These alkali metal salts can be easily removed by washing with water after soaking. The immersion conditions are not particularly limited, but considering the water resistance after immersion,
It is desirable to immerse at 0 to 60°C for 70 minutes or more. By this method, borate is generally introduced in an amount of 0.005 to 0.1 times the equivalent of liquid crystal composition H.

(11) A method of precipitating a composition by dissolving a predetermined amount of a hydroxyl group-containing polymer and a linear organic compound in a solvent that dissolves them, and mixing this with an aqueous borate solution.

The solvent and borate aqueous solution used in this method are as described above (1
) is used to obtain [−.

The liquid crystalline composition of the present invention can be obtained by filtering the formed precipitate.

The method for quantifying linear organic compounds in the liquid crystal composition of the present invention is as follows:
The composition is extracted with a solvent in which the linear organic compound is soluble, and the solvent is distilled off (and determined by measuring the weight of the residue afterward. Borate concentration is determined by the method of quantifying boron element. Since this is generally difficult, it is determined by quantifying the a degree of a counter ion of boric acid, such as sodium ion or potassium ion, using fluorescent X-ray spectrometry or atomic absorption spectrometry.

The liquid crystalline composition of the present invention thus produced is generally a colorless, white or pale yellow solid. Also, 0 to 7
It is insoluble in water at 0°C and exhibits liquid crystallinity. The vortex range exhibiting liquid crystallinity is within the range of 12θ to 200°C, depending on the type and composition ratio of the linear organic compound.

The liquid crystallinity is generally confirmed by optical and/or thermal measurements. Optical fx measurements are generally confirmed by the anisotropic phase due to liquid crystal formation using a polarizing microscope.

Is it hot again? The 1411 constant includes, for example, measurement using a differential scanning calorimeter. As a result, if it is a liquid crystal, the amount of heat associated with the transition from solid to liquid crystal and the spectacular scenery associated with the transition from liquid crystal to isotropic liquid are observed, confirming liquid crystallinity. The liquid crystalline composition of the present invention exhibits liquid crystallinity and can be used, for example, in display devices, various sensors, experimental materials in biomembrane research, and the like.

Furthermore, one of the properties of the liquid crystalline composition of the present invention is that it has a unique substance permeation ability.

For example, in water permeation, the permeability changes rapidly after reaching a certain temperature. This indicates that the liquid crystal composition of the present invention is useful as a valve that opens and closes depending on temperature. This property is a property that is first expressed in the liquid crystal composition of the present invention.

As described above, the liquid crystal composition of the present invention immobilizes an organic compound having a function similar to that of bovine body membranes,
It is extremely easy to handle. Furthermore, even when used in water, there is extremely little elution of linear organic compounds, and it exhibits liquid crystallinity over a long period of time.

Examples will be given below to further specifically explain the present invention, but the present invention is not limited to these Examples.

Example 1 A soap-like solution was obtained by ultrasonically dispersing Compound 20 in a water bottle D. Polyvinyl alcohol (viscosity average molecular weight %) goljki with water qIILl! dissolved in. After mixing both, place #i in a glass chalet with a diameter of 6 cm.
Treated.

Water is evaporated under conditions of 20°C and atmospheric pressure to a thickness of s.

A uniform transparent film-like material of μm size was obtained. Is this film-like substance sodium tetraborate-2? s It was immersed in an aqueous solution containing potassium bromide atoms v/θθtxlVc23c for 72 hours.

After removing this and thoroughly washing with water to completely remove potassium bromide, a transparent film-like material was obtained by drying under reduced pressure. According to elemental analysis, the composition ratio (linear organic compound/hydroxyl group-containing polymer, weight ratio) is n. The value of S was obtained. Also,
By fluorescent X-ray analysis of potassium atoms, a value of 0.022 was obtained as a composition ratio (borate/-(-CI-12G)++ unit 0 days, residual ratio).

When this film-like substance was observed with a polarized Th microscope, an anisotropic phase was observed. In addition, when the temperature is increased using a differential scanning calorimeter,
3C in air and water, respectively.

An endotherm of crystal-to-liquid crystal transition was observed in Da 7c. When this film-like material was immersed in 2SC water for 2q hours and the weight change was measured, the weight loss was 0. ．． It was 7%. In addition, after immersing this film-like material in water at tO'C for 1 hour, the degree of swelling was determined from the change in area. It was ψ times. At that time, the change in weight f' (il) was measured and the weight loss was 0.3%.For comparison, a membrane material that had not been immersed in the boric acid aqueous solution was immersed in water at 60°C for 7 hours. As a result, it was completely dissolved in water.Also, 1. ]? A film-like substance consisting only of IJ vinyl alcohol was similarly treated with an aqueous borate solution, and the obtained film-like substance was filtered in water at 0°C for 7 hours. When it was immersed, it completely dissolved in water. From the above, it was revealed that the liquid crystalline composition of the present invention is a stabilized composition whose constituent components do not dissolve even in water at 6θ°C.

Example 2 A soap-like solution was obtained by ultrasonically dispersing the compound in water/θrnl in the amount shown in Table 1. Polyvinyl alcohol (viscosity 乎H wt %) was dissolved in 10 CCIIC of water in the indicated amount. After mixing both, the water was evaporated under the conditions shown in Figure 1 to obtain a transparent film. This film-like substance is dissolved in potassium tetraborate 2
t, aqueous solution containing potassium bromide/θV/θ0txlK2
! ; Soaked at ℃ for 12 hours. This was taken out, thoroughly washed with water to completely remove potassium bromide, and then dried under reduced pressure to obtain a transparent film-like material. The results are shown in Table 1. Regarding these film-like substances, it was confirmed that they showed several properties by the same method as in Example 1.
When immersed in water of C, the weight loss was all 0.5%.
It was within

Example 3 Compound 209 was ultrasonically dispersed in 1 ml of water, and a soapy solution of 0 mg was dissolved in 1 ml of water. After mixing both, the mixture was cast into a glass petri dish with a diameter of A cm. Water was evaporated under conditions of 2θ°C and atmospheric pressure to obtain a film-like substance.

This film-like material was immersed in IOθml of an aqueous solution containing the borate and electrolyte shown in Table 2 under the conditions shown in Table 2.

After removing this and thoroughly washing with water to completely remove the electrolyte, a transparent film-like material was obtained by drying under reduced pressure.

By elemental analysis, values of / and S were obtained as composition ratios (@ chain organic compound/hydroxyl group-containing polymer, weight ratio). The results are shown in Table 2. It was confirmed that these films and materials exhibited liquid crystallinity by the same method as in Example.

Also, when immersed in 2SC water, the weight loss was 7.
It was within 0%.

Example 1 A film-like material was obtained in the same manner as in Example 1, except that the linear organic compound shown in Table 3 was used and θ Misaki was used as the hydroxyl group polymer shown in Thorn 3. The results are shown in Table 3. It was confirmed by the same method as in Example 1 that these film-like materials exhibited bath properties. When the samples were immersed in water at 25°C in the same manner as in Example 1, all weight losses were within 7%.

Example 5 720 ml of the compound was ultrasonically dispersed in 6 ml of water to obtain a soap-like solution. Polyvinyl alcohol (viscosity average molecular %) gO
tryi was dissolved in water. After mixing both,
The mixture was cast into a glass Petri dish with a diameter of b cm. io water
c. Evaporated under atmospheric pressure to obtain a transparent film with a thickness of 57 μm. This film-like material was immersed in 100 parts of water containing 21 parts of potassium tetraborate and 10 parts of potassium bromide at 26°C for 70 hours. This was removed and the potassium bromide was completely removed by thorough washing with water, followed by drying under reduced pressure to obtain a transparent film-like material.

Elemental analysis gave a composition ratio (linear organic compound/hydroxyl group polymer, weight ratio) of /.3. Fluorescence X-ray analysis of the potassium atom yielded 0°θ, 23. When this film-like material was observed under a polarizing microscope, it was found that the grains were anisotropic. 1. Using a differential scanning calorimeter, crystals were measured to 27°C and 2/C in air and water at elevated temperatures, respectively.
An endotherm of bath crystal transition was observed. When this film-like material was immersed in water at 25° C. for 2 hours and the weight change was measured, the weight loss was 0.2%.

Example B Straight chain organic compound shown in Rokuda by the same method as Example S/2
A film-like substance is obtained from θ■ and the hydroxyl group polymer gθ cape shown in Table 9. This film-like material was immersed in a borate solution in the same manner as in Example 5 to obtain a transparent film-like material. The results are shown in Table 9. The liquid crystallinity of these film-like materials was confirmed in the same manner as in Example DA. When immersed in water at 25°C in the same manner as in Example S, all weight loss was 0. It was within the range.

Example 7 Compound 2110q was ultrasonically dispersed in lθ11Ll of water to obtain a soap-like solution. ,l? +7 vinyl alcohol (viscosity average %)/60η was dissolved in water gtxlK. After mixing both, the mixture was poured into a Teflon petri dish with a diameter of 2 cm.

Water is evaporated under conditions of /0'C and atmospheric pressure to a thickness of 9
A 5 μm transparent membranous vlJ was swallowed. This film-like material was immersed for 72 hours in 100 txl of an aqueous solution containing 21 tf of sodium tetraborate and 10 tf of sodium bromide.

This was removed, thoroughly washed with water to remove sodium bromide, and then dried under reduced pressure to combine with the transparent film wJ.

According to elemental analysis, the composition ratio (i-chain truncated compound/H-containing compound) + xyl group polymer, 1 ratio). The value of S was obtained. According to atomic absorption spectrometry of IJium atoms, O0θ/S
obtained the value of

When this film-like material was observed under a polarizing microscope, an anisotropic phase was observed. Furthermore, when the temperature was raised using a differential calorimetry needle, endotherms due to the crystal-liquid crystal transition were measured at 57°C and 97°C in nitrogen and water, respectively. Add this film-like substance to water at 25°C.
After soaking for a period of time, the weight change was measured and the weight loss was 0.
．． It was 7%.

Example Table A film-like material *J was obtained in the same manner as in Example 7, except that the direct-casting organic compound 2gθda shown in Table S and the hydroxyl group-containing polymer/Aθ■ shown in Table 5 were used. The results are shown in 6S. It was confirmed by the same method as in Example 7 that these film-like materials exhibited liquid crystallinity. In addition, in the same manner as in Example 7, 2SC
When immersed in water, the weight loss was all within 0.5%.

Example W compound, ? AO1nq was ultrasonically dispersed in water/gtai to obtain a soap-like solution. Polyvinyl alcohol f viscosity average molecular weight: /s 1,000-f CH2-CH-3- Unit: 9
9,? miiH%), 2t1tOη was dissolved in water/2tttl. After mixing both, the mixture was poured into a glass petri dish with a diameter/θ scratch.

Water, 2! A film-like product was obtained by evaporation under rC% atmospheric pressure conditions. This film was immersed in an aqueous solution containing 21 sodium tetraborate and 10 f/'ft of sodium sulfate at θ°C for an hour. This was thoroughly washed with water and sulfuric acid) After completely removing the IJium, it was dried under reduced pressure to leave a transparent film. By elemental analysis, the composition ratio (linear organic compound/hydroxyl group polymer, weight) /, 3-
obtained the value of In addition, by atomic absorption analysis of sodium atoms, the H values of θ and θ were obtained as the composition ratio (borate/-(-CH2Cl) unit, equivalent ratio). This film-like vlJ was observed with a polarizing microscope. However, an anisotropic phase was observed, and a differential scanning calorimeter showed that an anisotropic phase of 33C and 1I in air and water, respectively, was observed when the temperature was increased.
An endotherm of crystal-liquid crystal transition was observed in gc. 25. After being immersed in C water for 2 q hours, the N sound quality was measured and the heavy capacitance was θ, θ.

Example/θ Example 9 except that the +M order organic compound 310■ shown in Table 6 and the hydroxyl group-containing polymer 2110■ shown in Table 6 were used.
Membrane-like vlJ was obtained in the same manner. The results are shown in Table 6.

It was confirmed that these film-like materials exhibited liquid crystallinity using the same method as in Example 2.

In addition, when immersed in water at 25'C in the same manner as in Example 9, all weight losses were within θ and g.

Example No Compound/fff was dispersed by ultrasonic waves in 50 cc of water to obtain a soap-like solution. Polyvinyl alcohol (viscosity average molecule 0, 7
1 was dissolved in water Sθσ. Mix the two to form an aqueous solution containing 21 sodium tetraborate and 100 sodium bromide lθ1.
It was discharged from the capillary into wn1l and left in co5c for 12 hours. The deposited precipitate was collected by filtering, thoroughly washed with water, and then dried under reduced pressure to obtain a transparent fibrous composition. The value of the composition ratio (linear organic compound/hydroxyl group polymer, weight ratio/!i) was obtained by the original analysis. In addition, the composition ratio (borate/ (
-CH2CH+ unit, equivalent ratio], the value of θ and θ3s is 0 days. When this composition was observed under a polarizing microscope, an anisotropic phase was observed. Also, using a differential scanning calorimeter, when the temperature was raised in air and water, 4 tc and 4 tc, respectively, were observed.
An endotherm of 7cK crystal-several transition was observed. If this composition was immersed in 2SC water for 2V hours, the weight change would be 4 (]
When tested, the weight loss was θ, /chi.

Example 12 Linear organic compounds shown in Table 7 were prepared in the same manner as in Example 1.
V and the hydroxyl group-containing polymer θ shown in Table 7. A mixed bath was obtained from A7ft. Are these mixed slang? Contribution plJ/
The mixture was mixed with a borate solution in the same manner as in 4 to form a fibrous atom. Chomai is shown in 67.

Accuracy of these compositions was ensured in the same manner as in the example series //. Also, in the same manner as Example //, 2SC
When immersed in water, all M key ranges were 1. It was within s%.

1A Example/3 The film-like material obtained in the previous example/2. Acm2
Stainless steel cell (Toyo Kagaku KST-'17)
and filled the cell with distilled water. This is all normal perpeno ration equipment * (rDuJ, star (3), 77g
(19g3) (6)
K) Measure the amount of permeation of water using the No. 10-Page Mothering Method at each temperature shown in Table g while keeping the pressure on the vacuum side at 0.5 mmHf1, and find the permeation coefficient. The results are shown in Figure g.

As shown in Table g, it has become clear that the membrane material of the present invention can reversibly change its permeability coefficient significantly beyond 9t°C.

Claims (1)

[Claims] (1) (i) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A polymer having a repeating unit shown by (ii) (a) 2 or 3 straight-chain hydrophobic groups, or (
(b) an organic compound having at least one linear hydrophobic group containing a rigid moiety in the chain, and (c) having a quaternary ammonium group. and (iii) a liquid crystalline composition comprising a borate.